WO2020130282A1 - Élément thermoélectrique et pâte à braser comprise dans celui-ci - Google Patents

Élément thermoélectrique et pâte à braser comprise dans celui-ci Download PDF

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Publication number
WO2020130282A1
WO2020130282A1 PCT/KR2019/011071 KR2019011071W WO2020130282A1 WO 2020130282 A1 WO2020130282 A1 WO 2020130282A1 KR 2019011071 W KR2019011071 W KR 2019011071W WO 2020130282 A1 WO2020130282 A1 WO 2020130282A1
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Prior art keywords
substrate
thermoelectric
electrode
metal
thermoelectric element
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PCT/KR2019/011071
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English (en)
Korean (ko)
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박주현
양승호
양승진
황병진
연병훈
손경현
박정구
장봉중
이태희
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엘티메탈 주식회사
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Priority claimed from KR1020190034437A external-priority patent/KR102149098B1/ko
Application filed by 엘티메탈 주식회사 filed Critical 엘티메탈 주식회사
Publication of WO2020130282A1 publication Critical patent/WO2020130282A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/81—Structural details of the junction
    • H10N10/817—Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions

Definitions

  • the present invention relates to a thermoelectric element and a solder paste included in the thermoelectric element, and more particularly, to a thermoelectric element having improved thermoelectric properties, such as output improvement and high temperature reliability, according to a material change of a bonding material.
  • thermoelectric elements and thermoelectric modules have been actively conducted in order to solve problems such as a sudden increase in the cost of energy-related resources and environmental pollution. These are applied to thermoelectric power generation such as waste heat generation or active cooling.
  • thermoelectric element is composed of a thermoelectric leg, an electrode, and a substrate, and an N-type semiconductor and a P-type semiconductor are used as the thermoelectric leg. After arranging a plurality of pairs of N-type and P-type semiconductors on a flat surface, they are connected in series using a metal electrode to form a thermoelectric element, which is then joined using a solder paste for bonding.
  • solder pastes containing lead (Pb) cannot be used due to RoHS harmful substances. Accordingly, SnAg alloy-based, SnAgCu-based, and SnAgBi-based solder pastes are mainly used.
  • SAC305 and SAC405 which are mainly used as solder pastes, are applied, a Cu 3 Sn phase is supersaturated on the surface of a copper (Cu) electrode, and a Cu 6 Sn 3 phase is deposited thereon.
  • electrical characteristics are deteriorated and the output of the thermoelectric element is lowered, and thermal mismatching causes cracks at the interface, resulting in high-temperature reliability of the element. Can adversely affect
  • the present invention has been devised to solve the above-mentioned problems, and it is a technical problem to provide a thermoelectric element having improved thermoelectric properties such as output improvement and high temperature reliability through a material change of a conventional Sn-based bonding material and a solder paste contained therein. do.
  • the present invention is a first substrate; A second substrate facing the first substrate; A first electrode and a second electrode respectively disposed between the first substrate and the second substrate; And a plurality of thermoelectric legs interposed between the first electrode and the second electrode. And a bonding material disposed between at least one of the first electrode and the thermoelectric leg and between the thermoelectric leg and the second electrode, wherein the bonding material includes Sn-based solder; And a metal dendrite having an average branch length of 5 to 50 ⁇ m.
  • the metal dendrites have one main axis, and a plurality of branched branches diverge from the main axis, but may satisfy at least two of the following conditions (i) to (iv).
  • the major axis has a long diameter of 5 to 50 ⁇ m
  • the longest branch of the plurality of branches has a length of 5 to 30 ⁇ m
  • the number of branches (number of branches/long diameter) with respect to the major diameter of the main shaft is 0.5 to 10/ ⁇ m
  • the average particle diameter (D 50 ) is 5 to 50 ⁇ m.
  • the metal dendrite may have a specific surface area measured by a BET measurement method of 0.4 to 3.0 m 2 /g, an apparent density of 0.5 to 1.5 g/cm 3, and an oxygen content of 0.35%. It may be:
  • the metal dendrites may be copper (Cu) dendrites, silver (Ag) coated copper dendrites, or mixtures thereof.
  • the copper dendrite has an average branched length of 5 to 20 ⁇ m, and may be included in 1 to 40% by weight based on the total weight of the bonding material.
  • the silver (Ag) coated copper dendrite has an average branch length of 5 to 20 ⁇ m, and may be included in an amount of 10 to 30% by weight based on the total weight of the bonding material.
  • the Sn-based solder is Sn; And metals of at least one of Pb, Al, and Zn.
  • the first substrate and the second substrate are the same as or different from each other, and each may be a ceramic substrate or a conductive substrate independently.
  • the conductive substrate a metal substrate; And an insulating layer formed on one surface thereof.
  • the insulating layer may include an insulating resin, or the insulating resin and a ceramic filler.
  • the first substrate, the second substrate, the first electrode, or the second electrode is the same as or different from each other, aluminum (Al), zinc (Zn), copper (Cu), It may include at least one metal of nickel (Ni) and cobalt (Co).
  • the first substrate and the second substrate are each conductive substrates
  • at least one of the conductive substrates is formed with a plurality of slits formed by being spaced apart at predetermined intervals along the longitudinal direction of the substrate ( Slit).
  • the conductive substrate provided with the plurality of slits may be a heating part.
  • thermoelectric leg is Bi-Te-based, Co-Sb-based, Pb-Te-based, Ge-Tb-based, Si-Ge-based, Sb-Te-based, Sm-Co-based, transition metal It may include at least one thermoelectric material selected from silicide-based, skuttrudite-based, silicide-based, half heusler, and combinations thereof.
  • the present invention is Sn-based solder; And a metal dendrite having an average branch length of 5 to 50 ⁇ m, wherein the metal dendrite provides a solder paste containing 1 to 40% by weight based on the total weight of the composition.
  • the solder paste may be for bonding a metal and a dissimilar material in a temperature range of 250 to 400°C.
  • reliability of a product may be improved by using a solder paste in which metal dendrite is mixed in a predetermined blending ratio in Sn-based solder.
  • thermoelectric leg when a conventional Sn-based solder paste is used, a problem of a local alloy layer generated at an interface portion of an electrode (eg, a Cu electrode) is solved, and the electrical conductivity between the electrode and the thermoelectric leg is improved to improve thermoelectric properties. It can contribute to improvement and high temperature reliability.
  • an electrode eg, a Cu electrode
  • thermoelectric device 1 is a perspective view showing a thermoelectric device according to an embodiment of the present invention.
  • thermoelectric device 2 is a cross-sectional view of a thermoelectric device according to a first embodiment of the present invention.
  • thermoelectric device 3 is a cross-sectional view of a thermoelectric device according to a second embodiment of the present invention.
  • FIG. 4 is a plan view of a conductive first substrate and a conductive second substrate, each of which is provided with a patterned first electrode and a second electrode according to an embodiment of the present invention.
  • thermoelectric device 5 is a cross-sectional view of a thermoelectric device according to a third embodiment of the present invention.
  • thermoelectric device 6 is a cross-sectional view of a thermoelectric device according to a fourth embodiment of the present invention.
  • FIG. 7 is a plan view of a conductive first substrate and a conductive second substrate provided with a patterned first electrode, a second electrode, and a plurality of slits according to another embodiment of the present invention.
  • FIG. 8 is a schematic view showing the structure of a metal dendrite according to the present invention.
  • FIG 11 is an image of a bonding layer formed by applying a solder paste (SAC305) according to an embodiment of the present invention.
  • SAC305 solder paste
  • thermoelectric device 12 is an interface image (magnification of 5,000) between an electrode and a bonding layer in a thermoelectric device according to an embodiment of the present invention.
  • thermoelectric element 100, 200, 300, 400: thermoelectric element
  • planar this means when the target portion is viewed from above, and when it is referred to as “cross-sectional”, it means when the cross section of the target portion vertically cut is viewed from the side.
  • the Sn-based solder used in the existing thermoelectric element generates a local alloy layer at the interface portion of the electrode (eg, Cu electrode), and the electrical characteristics are reduced due to the difference in electrical conductivity between these alloy layers and the output of the thermoelectric element is lowered. Is effected as a necessity.
  • thermoelectric properties such as improving the output of the thermoelectric element and high temperature reliability
  • it is characterized by changing the material of the solder paste constituting the thermoelectric element.
  • Sn-based solder solder
  • a dendrite-shaped metal powder eg, Cu dendrite
  • a solder paste in which they are mixed at a predetermined mixing ratio is applied as a bonding material.
  • the metal dendrite powder is located inside the bonding material, the Cu 3 Sn phase supersaturated at the interface of the electrode (for example, the Cu electrode) is suppressed, and Sn is reacted on the surface of the metal dendrite having a large specific surface area. It can be consumed and the portion generated in the Cu electrode can be suppressed as much as possible. That is, the metal dendrites act to prevent supersaturation in the Sn-based solder.
  • the metal dendrites are located between an electrode (for example, a Cu electrode) and a thermoelectric leg, and thus serve as a path for improving electrical conductivity, thereby lowering the electrical resistance of the thermoelectric element and increasing the output value.
  • the metal dendrites containing a plurality of branched shapes have a larger number of contact points between the particles than the spherical copper particles, the conductive properties are improved even when the amount of the conductive metal component is reduced, which is advantageous in terms of conductivity.
  • the bonding material (Sn-based solder paste) according to the present invention significantly improves the electrical conductivity between the thermoelectric leg and the electrode (e.g., Cu electrode) compared to the conventionally used Sn-based solder, and is applied to the interface portion of the Cu electrode.
  • thermoelectric element of the present invention includes both thermoelectric power generation and/or cooling elements.
  • thermoelectric element includes: two substrates facing each other; Conductive electrodes and thermoelectric materials (thermoelectric legs) disposed on upper and lower portions of the two substrates, respectively; And a bonding layer disposed between the thermoelectric material and the conductive electrode.
  • the bonding layer a bonding material in which Sn-based solder and metal dendrites are mixed at a predetermined mixing ratio is applied, and heat-treated at a high temperature to form a final thermoelectric element.
  • thermoelectric device according to the present invention.
  • the embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.
  • FIG. 1 is a perspective view schematically showing a structure of a thermoelectric element 100 according to a first embodiment of the present invention
  • FIG. 2 is a cross-sectional view of the thermoelectric element 100.
  • the thermoelectric element 100 includes: a first substrate 11; A second substrate 11 disposed opposite to the first substrate 11; A first electrode 20a and a second electrode 20b respectively disposed between the first substrate 11 and the second substrate 11; A plurality of thermoelectric legs 30 interposed between the first electrode 20a and the second electrode 20b; And a bonding material 40 disposed between at least one of the first electrode 20a and the thermoelectric leg 30 and between the thermoelectric leg 30 and the second electrode 20b.
  • thermoelectric element As in this specification, each configuration of the thermoelectric element will be described in detail as follows.
  • first substrate 11 and the second substrate 11 causes an exothermic or endothermic reaction when power is applied to the thermoelectric element 100, and may be made of a conventional electrical insulating material known in the art.
  • the first substrate 11 and the second substrate 11 may be ceramic substrates composed of one or more of Al 2 O 3 , AlN, SiC, and ZrO 2 , respectively. Or it may be composed of a high heat-resistant insulating resin or engineering plastic.
  • Each of the first substrate 11 and the second substrate 11 may have a flat plate shape, and is not particularly limited in size or thickness.
  • the thickness of each of the first substrate 11 and the second substrate 11 may be 0.5 to 2 mm, preferably 0.5 to 1.5 mm, and more preferably 0.6 to 0.8 mm.
  • One of the two substrates is a cold side substrate in which an endothermic reaction occurs, and a heat pad may be applied to the substrate.
  • the heat dissipation pad may be formed of a silicone polymer or an acrylic polymer, and may have a thermal conductivity in the range of 0.5 to 5.0 W/mk to maximize heat transfer efficiency. It can also act as an insulator.
  • the other of the two substrates may be a hot side substrate.
  • the first electrode 20a and the second electrode 20b are disposed on the first substrate 11 and the second substrate 11, which are disposed to face each other. That is, the second electrode 20b is disposed at a position facing the first electrode 20a.
  • first electrode 20a and the second electrode 20b are not particularly limited, and materials used as electrodes in the art may be used without limitation.
  • the first electrode 20a and the second electrode 20b are the same or different from each other, and each independently aluminum (Al), zinc (Zn), copper (Cu), nickel (Ni), and cobalt At least one metal of (Co) can be used.
  • Al aluminum
  • Zn zinc
  • Cu copper
  • Ni nickel
  • Co cobalt
  • At least one metal of (Co) can be used.
  • nickel, gold, silver, titanium, and the like may be further included. Its size can also be varied.
  • it may be a copper (Cu) electrode.
  • the first electrode 20a and the second electrode 20b may be patterned into a predetermined shape, and the shape is not particularly limited. For example, it may have a pattern shape as shown in Figure 4 (a) and Figure 4 (b).
  • a method of patterning the first electrode 20a and the second electrode 20b a conventionally known patterning method can be used without limitation. For example, a lift-off semiconductor process, a deposition method, a photolithography method, or the like can be used.
  • thermoelectric legs 30 are interposed between the first electrode 20a and the second electrode 20b.
  • thermoelectric legs 30 include a plurality of P-type thermoelectric legs 30a and N-type thermoelectric legs 30b, which are alternately arranged in one direction. In this way, the upper and lower surfaces of the P-type thermoelectric legs 30a and N-type thermoelectric legs 30b neighboring in one direction are electrically connected in series with the first electrode 20a and the second electrode 20b, respectively.
  • Each of these thermoelectric legs 30a, 30b includes a thermoelectric semiconductor substrate.
  • thermoelectric semiconductor included in the thermoelectric leg 30 may be formed of a conventional material in the art where temperature is generated at both ends when electricity is applied or electricity is generated when the temperature difference is generated at both ends.
  • thermoelectric semiconductors including at least one element selected from the group consisting of transition metals, rare earth elements, group 13 elements, group 14 elements, group 15 elements, and group 16 elements may be used.
  • examples of rare earth elements include Y, Ce, La, etc.
  • examples of the transition metal include Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Ag, and Re may be one or more
  • examples of the Group 13 element may be one or more of B, Al, Ga, and In
  • examples of the Group 14 element may be C, Si, Ge, Sn, and Pb. It may be one or more, and examples of the group 15 element may be one or more of P, As, Sb, and Bi
  • examples of the group 16 element may use one or more of S, Se, and Te.
  • thermoelectric semiconductor As a thermoelectric semiconductor that can be used, it can be made of a composition containing at least two or more of bismuth (Bi), telelium (Te), cobalt (Co), samarium (Sb), indium (In), and cerium (Ce).
  • Bi-Te-based thermoelectric semiconductors may include (Bi,Sb) 2 (Te,Se) 3 thermoelectric semiconductors in which Sb and Se are used as a dopant, and CoSb as a Co-Sb thermoelectric semiconductor.
  • Three -type thermoelectric semiconductors can be exemplified, AgSbTe 2 and CuSbTe 2 can be exemplified as Sb-Te-based thermoelectric semiconductors, and PbTe, (PbTe)mAgSbTe 2 and the like can be exemplified as Pb-Te-based thermoelectric semiconductors.
  • it may be composed of a Bi-Te-based or CoSb-based thermoelectric material.
  • thermoelectric semiconductor may be particles having a predetermined size, for example, may have an average particle diameter in the range of about 0.01 to about 100 ⁇ m.
  • thermoelectric semiconductor can be manufactured in various ways, and is not particularly limited.
  • the thermoelectric semiconductor may be manufactured by sequentially performing a pressure sintering method after performing a melt-spining method or a gas atomization method.
  • the thermoelectric leg 30 including the P-type thermoelectric leg 30a and the N-type thermoelectric leg 30b may be formed into a predetermined shape, such as a rectangular parallelepiped, by a method such as cutting, and applied to the thermoelectric element.
  • thermoelectric element 100 includes: between the first electrode 20a and the thermoelectric leg 30; And at least one of the thermoelectric leg 30 and the second electrode 20b, preferably a bonding material 40 disposed between all of them.
  • the bonding material is characterized in that it contains a metal powder in the form of a dendrite (dendrite) in a common Sn-based solder known in the art.
  • the metal dendrites have one main axis when observed with an electron microscope (100 to 20,000 magnification), and a plurality of branched branches from the main axis vertically or obliquely branch, or two-dimensional or It is a conductive metal particle having a three-dimensionally grown shape.
  • the main axis indicates a rod-like portion on which a plurality of branches are branched.
  • the average branch length of the metal dendrites is not particularly limited, and is, for example, 5 to 50 ⁇ m, and preferably 5 to 30 ⁇ m.
  • the metal dendrites of the present invention preferably exhibit a dendrite phase that satisfies at least two of the following conditions (i) to (iv) when observed with an electron microscope (500 to 20,000 magnification).
  • the long axis length of the main shaft means the total length of the main shaft, and may be 5 to 50 ⁇ m, and specifically 5 to 30 ⁇ m.
  • the longest branch length among the plurality of branch shapes means the length of the longest branch among the branches extending from the main axis, and indicates the growth degree of dendrites. In one example, it may be 5 to 30 ⁇ m, specifically 10 to 25 ⁇ m.
  • the number of branches (number of branches/longer diameter) with respect to the major diameter of the main shaft indicates the number of branches of dendrites, and may be 0.5 to 10/ ⁇ m, and specifically 1 to 8/ ⁇ m.
  • the average particle diameter (D 50 ) refers to a two-dimensional size including the long diameter of the dendrites, and may be 5 to 50 ⁇ m, and specifically 5 to 30 ⁇ m.
  • the main shaft thickness of the dendrites may be 0.3 to 5.0 ⁇ m.
  • the metal dendrites of the present invention have a higher specific surface area than spherical metal particles as they have the aforementioned structural characteristics.
  • the metal dendrite may have a specific surface area measured by a BET measurement method of 0.4 to 3.0 m 2 /g, and specifically 0.5 to 2.0 m 2 /g. If the specific surface area of the metal dendrites is significantly small, the branches do not develop, and since they are close to a pine cone to a spherical shape, it is difficult to obtain the effect of the dendrites copper powder.
  • the metal dendrite may have an apparent density of 0.5 to 1.5 g/cm 3, and an oxygen content of 0.35% or less is suitable.
  • the metal dendrite according to the present invention is not particularly limited to the metal material to be used if it has electrical conductivity and satisfies the structural characteristics and physical properties described above.
  • copper dendrite (Cu dendrite), silver (Ag) coated copper dendrite (Ag coated Cu dendrite), or a mixture thereof may be used.
  • copper (Cu) is preferable because it is not only similar in electrical conductivity to silver (Ag) but also economical.
  • the content of the metal dendrites is not particularly limited, and for example, may be included in 1 to 40% by weight based on the total weight of the bonding material, preferably 5 to 30% by weight.
  • the content of such copper dendrites is 1 to 40 weight compared to the total weight of the bonding material %, preferably 5 to 30% by weight.
  • metal dendrites use silver (Ag) coated copper dendrites having an average branch length of 5 to 20 ⁇ m, preferably 10 to 30 ⁇ m, compared to the total weight of the bonding material It is preferably included in the range of 10 to 30% by weight.
  • the metal dendrites can be used alone as the bonding material component, and it is also included in the scope of the present invention to mix the metal powder having various materials, particle sizes, and/or shapes as a bonding material component.
  • the above-mentioned metal dendrites and one or more metal powders such as spherical, acicular, flake, and amorphous may be mixed.
  • the Sn-based solder mixed with the above-mentioned metal dendrites may use a common Sn-based solder component known in the art.
  • the Sn-based solder is Sn; It may have a composition including at least one metal of Pb, Al, and Zn. .
  • thermoelectric element 100 of the present invention is between the first electrode 20a and the thermoelectric leg 30; And a diffusion barrier layer (not shown) disposed between the thermoelectric leg 30 and the second electrode 20b.
  • the diffusion barrier layer can be used without limitation, conventional components known in the art, for example, at least one selected from the group consisting of tantalum (Ta), tungsten (W), molybdenum (Mo) and titanium (Ti) can do.
  • the first electrode 20a and the second electrode 20b may be electrically connected to a power supply.
  • a DC voltage When a DC voltage is applied from the outside, the holes of the p-type thermoelectric leg 30a and the electrons of the n-type thermoelectric leg 30b move, so that heat and endothermic heat may occur at both ends of the thermoelectric leg.
  • thermoelectric device 100 In the thermoelectric device 100 according to another embodiment of the present invention, at least one of the first electrode 20a and the second electrode 20b may be exposed to a heat source. When heat is supplied by an external heat source, electrons and holes move, and current flows in the thermoelectric element, thereby generating electricity.
  • thermoelectric element according to the first embodiment described above may be manufactured according to a method known in the art.
  • a manufacturing method For an example of such a manufacturing method, (a) preparing two insulating substrates; (b) forming a first electrode and a second electrode on one surface of the two insulating substrates, respectively; And (c) placing the first electrode and the second electrode so as to face each other, and then placing a plurality of thermoelectric legs therebetween and bonding using the bonding material.
  • the manufacturing method is not limited only by the following method or order, and the steps of each process may be modified or selectively mixed as necessary.
  • thermoelectric leg As an example of a method of manufacturing a thermoelectric leg using a thermoelectric material in the above manufacturing method, Bi-Te or CoSb-based thermoelectric material is melted using an RSP and then manufactured by ribbon or after mixing raw material powders and then firing such as heat treatment 1 It forms a phase. After sintering through hot press and discharge plasma sintering (Spark Plasma Sintering) to form a sintered body, slicing is performed according to the desired thickness, and lapping is performed according to the final thickness to increase the height of the material. Adjust within 1/100.
  • a thermoelectric leg is manufactured by subjecting the surface of the thermoelectric material having stepped control to surface coatings such as Co, Ni, Cr, and W, and finally dicing according to the size of the material.
  • a ceramic substrate such as Al 2 O 3 , AlN, SiC, and ZrO 2 is used, and a Cu electrode pattern is formed on one surface of the substrate, followed by heat treatment to fix it.
  • thermoelectric legs are disposed and bonded between the first electrode and the second electrode using the thermoelectric legs and substrate prepared as described above.
  • a bonding material include Sn-based solders; And a Sn-based solder paste in which metal dendrite is included at a predetermined mixing ratio.
  • a bonding material paste is applied to a pattern of the first electrode 20a with a predetermined thickness, and n-type and p-type thermoelectric legs are arranged thereon.
  • the final configuration is completed by arranging the previously formed n-type and p-type thermoelectric legs in a portion where only the bonding material is applied.
  • heat treatment is performed at 300 to 500° C. to final bonding, and then electric wires are connected to complete manufacturing of the thermoelectric element.
  • thermoelectric leg and the thermoelectric element including the same may be provided in, for example, a thermoelectric cooling system or a thermoelectric power generation system.
  • the thermoelectric power generation system means a normal system that generates power by using a temperature difference, and examples thereof include a waste heat furnace, a vehicle thermoelectric power generation system, and a solar thermoelectric power generation system.
  • the thermoelectric cooling system may include, but is not limited to, a micro cooling system, a general purpose cooling device, an air conditioner, and a waste heat power generation system.
  • the thermoelectric element using Sn-based solder at 250 to 400°C is not particularly limited.
  • thermoelectric power generation system and the thermoelectric cooling system are known in the art, and thus, detailed description is omitted. Also, in the present invention, even though they are denoted by the same reference numerals, they may have different configurations from each other.
  • thermoelectric element 200 is a cross-sectional view schematically showing a cross-section of a thermoelectric element 200 according to a second embodiment of the present invention. 3, the same reference numerals as those in FIGS. 1 to 2 denote the same members.
  • thermoelectric element 200 is insulated on one surface of the metal substrates 11a and 11b compared to FIGS. 1 to 2 using the insulating ceramic substrate 11
  • the conductive substrates 10a, 10b on which the layers 12a, 12b are formed are used.
  • thermoelectric element 200 includes: a conductive first substrate 11a; A first insulating layer 12a formed on one surface of the conductive first substrate 11a; A first electrode 20a disposed on the first insulating layer 12a; A second electrode 20b disposed opposite to the first electrode 20a; A plurality of thermoelectric legs 30 interposed between the first electrode 20a and the second electrode 20b; And a bonding material 40 disposed between at least one of the first electrode 20a and the thermoelectric leg 30 and between the thermoelectric leg 30 and the second electrode 20b.
  • the conductive first substrate 11a and the conductive second substrate 11b cause an exothermic or endothermic reaction when power is applied to the thermoelectric element 100. These may be the same as or different from each other, and each may be made of a conventional conductive metal material known in the art.
  • the conductive first substrate 11a may include at least one metal among aluminum (Al), zinc (Zn), copper (Cu), nickel (Ni), and cobalt (Co).
  • the electrodes 20a and 20b are directly disposed on the conductive substrates 11a and 11b, they are electrically conductive, and an electrically insulating material must be interposed therebetween. Accordingly, the first insulating layer 12a is formed on one surface of the conductive first substrate 11a on which the first electrode 20a is disposed, and the conductive second substrate 11b on which the second electrode 20b is disposed. The second insulating layer 12b is formed on one surface.
  • the first insulating layer 12a and the second insulating layer 12b are disposed to face each other.
  • the first insulating layer 12a and the second insulating layer 12b may be the same or different from each other, and an easily insulating electrical insulating material may be used.
  • an insulating resin may be used alone, or a mixture of the insulating resin and a ceramic filler (powder) may be included.
  • the insulating resin may include at least one of a conventional thermosetting resin and a thermoplastic resin known in the art.
  • a heat-resistant resin having a glass transition temperature (Tg) of 250°C or higher, preferably 250 to 300°C. desirable.
  • thermosetting resin usable as the first insulating layer 12a and the second insulating layer 12b include epoxy resin, polyurethane resin, alkyd resin, phenol resin, melamine resin, silicone resin, urea resin, In the group consisting of vegetable oil modified phenolic resin, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, unsaturated polyester resin, furan resin, polyimide resin, cyanate resin, maleimide resin and benzocyclobutene resin It may be one or more selected. Specifically, the thermosetting resin may be at least one selected from the group consisting of epoxy resin, phenol resin, melamine resin, silicone resin, urethane resin and urea resin.
  • Epoxy resins can be used without limitation, conventional epoxy resins known in the art, it is preferable that two or more epoxy groups are present, without containing a halogen element in one molecule.
  • Non-limiting examples of usable epoxy resins include bisphenol A/F/S resin, phenol novolac epoxy resin, polyhydric phenol epoxy resin, novolac epoxy resin, alkylphenol novolac epoxy, biphenyl Type, aralkyl type, naphthol type, dicyclopentadiene type, or a mixed form thereof.
  • More specific examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, anthracene epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, and phenol novolac Type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol S novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol phenol coaxial novolac type epoxy resin , Naphthol corresol coaxial novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, triphenyl methane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene phenol addition reaction epoxy resin, phenol aral Kill type epoxy resin, polyfunctional phenol resin, naphthol aralkyl type epoxy resin, and the like.
  • the above-described epoxy resin may be used alone or in combination of two or more.
  • the high heat resistance epoxy resin is one containing at least one selected from phenol novolac epoxy resins and polyhydric phenol type epoxy resins.
  • the polyhydric phenol type epoxy resin refers to an epoxy resin having two or more average epoxy groups in the molecule, preferably 2 to 4.
  • thermoplastic resins include olefin resins, acrylic resins, rubbers, or mixtures thereof.
  • Specific examples include polyethylene, polypropylene, polystyrene, polyimide, teflon (PTFE), acrylonitrile-butadiene rubber (NBR), styrene butadiene rubber (SBR), acrylonitrile-butadiene-styrene rubber (ABS), carr Vxyl-terminated butadiene acrylonitrile rubber (CTBN), polybutadiene, styrene-butadiene-ethylene resin (SEBS), acrylic acid containing side chains having 1 to 8 carbon atoms ) And/or methacrylic acid ester resins (acrylic rubber), or mixtures of one or more thereof.
  • PTFE teflon
  • NBR acrylonitrile-butadiene rubber
  • SBR styrene butadiene rubber
  • ABS acrylonitrile-butadiene-
  • the above-mentioned thermoplastic resin contains the functional group which can react with the epoxy resin which is a thermosetting resin. Specifically, it is at least one functional group selected from the group consisting of an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methoxy group, and an isocyanate group. Since these functional groups form a strong bond with the epoxy resin, the heat resistance after curing is improved, which is preferable.
  • the first insulating layer 12a and the second insulating layer 12b may be epoxy resin layers each containing a ceramic filler.
  • the ceramic filler may use any conventional inorganic filler known in the art without limitation, and non-limiting examples of the ceramic filler usable include natural silica, fused silica, and amorphous silica.
  • Silica such as crystalline silica; Boehmite, alumina, talc, spherical glass, calcium carbonate, magnesium carbonate, magnesia, clay, calcium silicate, titanium oxide, antimony, glass fiber, aluminum borate, barium titanate, strontium titanate, calcium titanate , Magnesium titanate, bismuth titanate, barium zirconate, calcium zirconate, boron nitride, silicon nitride, or mica.
  • the above-mentioned powders may be used alone or in combination of two or more.
  • a filler in the form of a metal oxide such as aluminum oxide is used.
  • the average particle diameter (D 50 ) of the ceramic filler is not particularly limited, but in consideration of dispersibility, it is preferable that the average particle diameter is about 0.1 to 20 ⁇ m, specifically 0.5 to 15 ⁇ m. In addition, two or more types of ceramic fillers having different average particle diameters may be mixed.
  • the shape of the ceramic filler is also not particularly limited, and for example, it may have any shape selected from the group consisting of a spherical shape, a plate shape, a needle shape, a fiber shape, a branch shape, a conical shape, a pyramid shape, and an amorphous shape.
  • the ceramic filler may be used as it is by mixing with an epoxy resin, or a ceramic filler already surface-treated with an organic material may be used. This is because when using a ceramic filler surface-treated with an organic material, compatibility with a resin is excellent, and thus dielectric properties, heat resistance, and workability of the epoxy resin can be further improved.
  • the organic material is not particularly limited, and resins or silane coupling agents in the art may be used.
  • the method of surface-treating the ceramic filler with an organic material is not particularly limited, and a method of drying after adding the ceramic filler to a solution containing an organic material, for example, a vinyl group-containing silane coupling agent, may be mentioned.
  • the content of the ceramic filler may be appropriately adjusted in consideration of mechanical properties or other physical properties of the first insulating layer 12a and the second insulating layer 12b.
  • the content of the ceramic filler is 0 to 70 parts by weight, specifically 5 to 50 parts by weight, more specifically, based on 100 parts by weight of the epoxy resin constituting the first insulating layer 12a or the second insulating layer 12b Specifically, it may be 10 to 30 parts by weight.
  • the thickness of the above-described first insulating layer 12a and the second insulating layer 12b is not particularly limited, and can be appropriately adjusted within a range known in the art. These may be the same or different from each other.
  • the thickness of the first insulating layer 12a and the second insulating layer 12b may be 10 to 150 ⁇ m, respectively, and preferably 30 to 120 ⁇ m.
  • the first electrode 20a is disposed on the first insulating layer 12a formed as described above, and the second electrode 20b is positioned on a predetermined position of the second insulating layer 12b facing the first electrode 20a. ) Is placed.
  • the first electrode 20a and the second electrode 20b may be patterned in a predetermined shape, and the shape is not particularly limited. For example, it may have a pattern shape as shown in Figure 4 (a) and Figure 4 (b).
  • descriptions of materials, structures, and the like of each component may be applied as described in the thermoelectric element 100 according to the first embodiment of FIGS. 1 to 2.
  • thermoelectric device according to the second embodiment of the present invention may be manufactured according to a method known in the art, and for example, may be manufactured using a conventional metal foil and/or metal laminate with resin.
  • thermoelectric element In one embodiment of the method for manufacturing the thermoelectric element according to the second embodiment, (a) preparing two metal laminated plates having metal layers on both sides of an insulating layer; (b) forming a first electrode and a second electrode by etching each metal layer disposed on one surface of the two metal laminated plates; And (c) placing the first electrode and the second electrode so as to face each other, and then placing a plurality of thermoelectric legs therebetween and bonding using the bonding material.
  • a metal laminate plate to be used as a substrate for a thermoelectric element is prepared.
  • a form in which metal layers are stacked on both sides of the insulating layer as a center can be used without limitation.
  • the two metal layers may be composed of the same or different metal components from each other.
  • the two metal layer materials may be at least one metal of aluminum (Al), zinc (Zn), copper (Cu), nickel (Ni), and cobalt (Co).
  • One of the metal layers (for example, the first metal layer and the second metal layer) disposed on both sides of the metal laminated plate is used as a conductive first substrate, and the other forms a first electrode patterned in a predetermined shape through etching. Is done.
  • an etching method known in the art may be used as the etching method without limitation, and for example, physical etching, chemical etching, or a combination of both may be applied.
  • thermoelectric legs 30 are disposed on the patterned first electrode and the second electrode, and the bonding method is performed using a bonding material, the method of manufacturing the final thermoelectric element is the same as that of the first embodiment described above. Individual description of this is omitted.
  • thermoelectric element 300 is a cross-sectional view schematically showing a cross-section of a thermoelectric element 300 according to a third embodiment of the present invention.
  • the same reference numerals as in Figs. 1 to 3 denote the same members.
  • thermoelectric element 300 in the thermoelectric element 300 according to the third embodiment of the present invention, as compared with FIG. 3 using two conductive metal substrates, an insulating layer is formed on one surface as one of the conductive substrates, A conductive metal substrate having a plurality of slits on the other surface is used.
  • thermoelectric device when using a conventional electrically insulating ceramic-based substrate (eg, DBC) or manufacturing a thermoelectric device using a metal-based substrate, a phenomenon in which the output characteristics of the device deteriorates due to a difference in thermal expansion coefficient between materials.
  • a metal-based substrate when used, problems such as peeling of a thermoelectric leg and loss of output characteristics of a thermoelectric element may occur due to rapid thermal expansion of a metal material according to an increase in temperature of the thermoelectric element.
  • an insulating layer is formed on one surface as one of the two conductive substrates, and the temperature of the thermoelectric element is adopted by employing a conductive metal substrate provided with a plurality of slits on the other surface.
  • thermoelectric element 300 includes a conductive first substrate 11a having a first insulating layer 12a formed on one surface; A conductive second substrate 11b disposed opposite to the conductive first substrate 11a, a second insulating layer 12b formed on one surface, and provided with a plurality of slits 50 on the other surface; A first electrode 20a disposed on the first insulating layer 12a; A second electrode 20b disposed on the second insulating layer 12b; A plurality of thermoelectric legs 30 interposed between the first electrode 20a and the second electrode 20b; And a bonding material 40 disposed between at least one of the first electrode 20a and the thermoelectric leg 30 and between the thermoelectric leg 30 and the second electrode 20b.
  • the second insulating layer 12b Use a conductive substrate provided with a plurality of slits (50) spaced apart at predetermined intervals on the non-formed other surface.
  • the power generation power can be increased because it has a high temperature use temperature range, and the durability of the high temperature load is enhanced and excellent thermal stability is exhibited, resulting in a high final product. It can have reliability.
  • the conductive substrate provided with a plurality of slits is a substrate disposed on a hot side in order to exert the effect of providing flexibility during thermal expansion.
  • the metal substrate considering the thermal expansion characteristics of the metal substrate, it can be formed by appropriately adjusting the number or size of the slits 50.
  • the number of slits 50 formed on the second conductive substrate 11b is not particularly limited and may be appropriately adjusted according to the size of the substrate. For example, it may be a plurality of two or more, specifically 2 To dozens, more specifically 2 to 10 may be around.
  • a predetermined separation distance is formed between one of the slits 50 and the other slits adjacent thereto.
  • the separation distance between the plurality of slits 50 is not particularly limited, and may be appropriately adjusted in consideration of the thermal expansion characteristics of the metal substrate.
  • the separation distance between the plurality of slits 50 may be the same as or larger than the size corresponding to the plane of the first electrode 20a or the second electrode 20b, which will be described later, preferably a pair It may correspond to the size to form a unit cell, including the P-type thermoelectric leg (30a) and the N-type thermoelectric leg (30b). In one example, it may be 1.35 to 1.45 mm.
  • the plurality of slits 50 includes: a slit width formed along a first direction (eg, a longitudinal direction of the substrate); A slit length formed along a second direction intersecting the first direction; And a slit depth orthogonal to the first direction and the second direction and formed along a direction perpendicular to the conductive 1-2 substrates 11a and 11b (eg, a thickness direction of the substrate).
  • the plurality of slits 50 have substantially the same slit depth.
  • the depth of the slit is not particularly limited, and may be, for example, 70 to 90% based on the total thickness of the conductive first substrate 11a or the conductive second substrate 11b, respectively.
  • the length of the slit may be the same as the length in the longitudinal direction (first direction) and the vertical direction (second direction) of the conductive second substrate 11b, and the width of the slit may be conductive. It may be approximately 7 to 10% based on the total length along the length direction (first direction) of the 1-2 substrates 11a and 11b.
  • the depth of the slit is 0.49 to 0.63 mm
  • the slit width is 3.0 to 4.0 mm
  • the slit length is 40.5 mm.
  • the depth of the slit is 1.05 to 1.35 mm
  • the slit width is 3.0 to 4.0 mm
  • the slit length is 40.5 mm.
  • the plurality of slits 50 When viewing a horizontal cross-sectional shape, the plurality of slits 50 have a structure in which a plurality of intaglio patterns are regularly arranged.
  • the horizontal cross-sectional shape of the intaglio pattern is not particularly limited, and may be any one of a rectangle, a circle, an oval, a stripe, a rhombus, and a polygon, for example. In addition, various pattern shapes can be applied.
  • the plurality of slits 50 are formed on one surface of the conductive second substrate 11b on which the second insulating layer 12b is not formed, and preferably, the second insulating layer of the conductive second substrate 11b ( It is formed to be symmetrical with respect to the second electrode 20b disposed on 12b). Specifically, it may be arranged to have a horizontally symmetrical or centrosymmetrically structured structure based on a first direction line (eg, a long axis lengthwise direction of the second electrode) passing through the center of the second electrode 20b.
  • a first direction line eg, a long axis lengthwise direction of the second electrode
  • thermoelectric elements 100 and 200 are described in the thermoelectric elements 100 and 200 according to the first and second embodiments of FIGS. 1 to 3. It can be applied as is.
  • FIG. 6 is a cross-sectional view schematically showing a cross-section of a thermoelectric element 400 according to a fourth embodiment of the present invention.
  • the same reference numerals as in Figs. 1 to 5 denote the same members.
  • thermoelectric element 400 according to the fourth embodiment of the present invention and the embodiment of FIG. 5 using a conductive second substrate 11b provided with a plurality of slits 50 as an upper substrate
  • the conductive first substrate 11a provided with a plurality of slits 50 is used as the lower substrate.
  • the first insulating layer 12b is formed on one surface of the conductive first substrate 11a, and a plurality of slits 50 spaced apart at predetermined intervals on the other surface where the first electrode 20a is not disposed. It is provided. It is preferable that the conductive first substrate 11a is a hot side substrate in order to exert a softening effect during thermal expansion.
  • thermoelectric element 300 in the embodiment of FIG. 6, description of the material, structure, and the like of each component may be applied as it is to the description of the thermoelectric element 300 according to the third embodiment of FIG. 5, so a detailed description thereof will be omitted.
  • FIGS. 5 and 6 specifically illustrate an embodiment in which a plurality of slits 50 are formed on one of the conductive first substrate 11a and the conductive second substrate 11b, respectively.
  • the present invention is not limited thereto, and embodiments that are formed on both the conductive substrates 11a and 11b or are formed on the cross-section and/or both surfaces of the conductive substrates 11a and 11b also belong to the scope of the present invention.
  • FIGS. 3 to 6 employing a conductive metal substrate specifically illustrate an embodiment in which the first insulating layer 12a and the second insulating layer 12b are each formed of a single layer.
  • the present invention is not limited thereto, and the number, shape, and size of the insulating layers 12a and 12b are not particularly limited. That is, the configuration of the insulating layers 12a and 12b is not particularly limited, and can be freely deformed to have various shapes and sizes.
  • the insulating layers 12a and 12b may further include a conventional inorganic-based filler and/or organic-based filler known in the art within a range maintaining electrical insulation.
  • thermoelectric elements according to the third to fourth embodiments of the present invention may be manufactured according to a method known in the art, for example, using a conventional metal foil and/or metal laminate with a resin, preferably May be a copper clad laminate (CCL).
  • a conventional metal foil and/or metal laminate with a resin preferably May be a copper clad laminate (CCL).
  • thermoelectric device For an embodiment of the method for manufacturing the thermoelectric device according to the 3-4 embodiment, (a) preparing two metal laminated plates having metal layers on both sides of the insulating layer; (b) forming a first electrode and a second electrode by etching each metal layer disposed on one surface of the two metal laminated plates; (c) arranging the first electrode and the second electrode so as to face each other, and then placing a plurality of thermoelectric legs therebetween and bonding using the bonding material; And (d) a plurality of slits spaced apart at the same or greater intervals than the size corresponding to the plane of the first electrode or the second electrode, on the other surface of any one of the two metal laminated plates. It may be configured to include the step of forming.
  • a plurality of slits are formed on one surface of one of the two metal laminated plates.
  • a method of forming a plurality of slits is not particularly limited, and methods known in the art can be used without limitation. As an example, laser cutting, mechanical punching, or a cutting wheel may be used.
  • the separation distance between the plurality of slits can be adjusted to be equal to or larger than the size corresponding to the plane of the first electrode (or the second electrode) described above.
  • a plurality of slits, a plurality of thermoelectric elements that can be completed by a pair of P-type and N-type thermoelectric legs are connected to one thermoelectric element (eg, unit cell) as shown in FIG. 7 below
  • a unit region (not shown) may have a structure divided along the horizontal and vertical directions, and a sawing line may be formed at a boundary portion that partitions each unit region.
  • thermoelectric element after arranging a plurality of thermoelectric legs on a patterned first electrode and a second electrode and bonding using a bonding material is the same as the first to second embodiments described above. Individual description of this is omitted.
  • thermoelectric element using a metal laminated plate a method of manufacturing a thermoelectric element using a metal laminated plate is specifically described.
  • the present invention is not limited to this, and after applying an insulating resin such as an epoxy resin on a metal plate known in the art, forming a predetermined electrode pattern on the applied insulating layer, and then heat-treating and fixing it as a conductive substrate. Belongs to the category of
  • the present invention is Sn-based solder; And a metal dendrite having an average branch length of 5 to 50 ⁇ m, and the metal dendrite provides a solder paste containing 1 to 40% by weight based on the total weight of the composition.
  • the solder paste is a solder paste for joining metals and dissimilar materials in a temperature range of 250 to 400°C.
  • the heterogeneous material to be bonded to the metal is not particularly limited, and may be, for example, a conventional metal material known in the art, or a ceramic material or a thermoelectric semiconductor material. Since the detailed configuration of the above-described solder paste is the same as that of the bonding material of the thermoelectric element, individual descriptions thereof are omitted.
  • the device containing the Sn-based solder paste according to the present invention is not particularly limited, and includes all the electrochemical devices constructed using Sn-based solder paste at 250 to 400°C in the art.
  • Such an electrochemical device refers to all devices that undergo an electrochemical reaction, and specific examples include all types of primary, secondary cells, fuel cells, solar cells, capacitors, or thermoelectric devices. have. Preferably it may be a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding 99 wt% of Cu dendrite 1 wt% with a branching length of 10 to 20 ⁇ m onto a Cu electrode, and after placing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode with 95 wt% of Cu dendrite 5 wt% with a branching length of 10 to 20 ⁇ m added on a Cu electrode, and was constructed after raising a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding 10 wt% of Cu dendrite having a branching length of 10 to 20 ⁇ m to 90 wt%, and then constructing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding 20 wt% of Cu dendrite having a branching length of 10 to 20 ⁇ m to 80 wt%, and then constructing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding 30 wt% of Cu dendrite having a branching length of 10 to 20 ⁇ m to 70 wt%, and then constructing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding 60 wt% of Cu dendrite 40 wt% with a branching length of 10 to 20 ⁇ m onto a Cu electrode, and placing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding 50 wt% of Cu dendrite having a branching length of 10 to 20 ⁇ m on a Cu electrode, and placing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding 40 wt% of Cu dendrite 60 wt% having a branching length of 10 to 20 ⁇ m onto a Cu electrode, and placing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding 90 wt% of Ag coated Cu dendrite 10 wt% Ag coated 10% to 20 ⁇ m in length in the branch direction on the Cu electrode. It was constructed after the thermoelectric material was placed on top.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding 80 wt% Ag coated Cu dendrite 20 wt% Ag coated 10% to 20 ⁇ m in length in the branch direction on the Cu electrode. It was constructed after the thermoelectric material was placed on top.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding a 30% by weight Ag coated Cu dendrite coated with 10% Ag coated with 10 ⁇ 20 ⁇ m branch length to 70wt%. It was constructed after the thermoelectric material was placed on top.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding 10 wt% of Cu dendrite having a branching length of 20 to 30 ⁇ m to 90 wt%, and then constructing after placing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding 20 wt% of Cu dendrite having a branching length of 20 to 30 ⁇ m to 80 wt%, and then constructing after placing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated on a Cu electrode by adding a material with 30 wt% of Cu dendrite having a branching length of 20 to 30 ⁇ m to 70 wt%, and constructing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was applied after applying a 100 wt% bonding material on a Cu electrode and placing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • SAC305 (Sn-3.0Ag-0.5Cu) was coated with a bonding material composed of 80 wt% and 20 wt% of spherical Cu powder on a Cu electrode, and was constructed after placing a thermoelectric material thereon.
  • thermoelectric element was used to heat-treat at about 300 degrees, and the other side was coated with the same bonding material to produce a thermoelectric element.
  • Cu copper
  • the copper dendrite has a main shaft, has a dendritic shape in which a plurality of branched branches are branched from the main shaft, and the main shaft length (long axis size) is in the range of 10 to 20 ⁇ m.
  • FIG. 10 is an electron microscope image of copper (Cu) dendrites included in the bonding materials of Examples 12 to 14, and it can be seen that the major axis length (long axis size) of the copper dendrites is 20 to 30 ⁇ m.
  • FIG 11 is an image of a bonding layer formed by applying and drying a solder paste (SAC305) according to an embodiment of the present invention.
  • SAC305 solder paste
  • thermoelectric element manufactured using the bonding material of the present invention containing metal dendrites was evaluated as follows.
  • the bonding conditions were performed under a reflow of 370°C, a speed of 10 cm/min, and a nitrogen (N 2 ) gas atmosphere, and then using an electron microscope (SEM) to connect the bonding interface between the electrode-bonding layer-thermoelectric leg. Confirmed.
  • CuSn alloys size: about 6 to 8 ⁇ m
  • a plurality of metal dendrites included in the bonding layer firmly fix the thermoelectric leg and the Cu electrode. It was confirmed that the bridge (bridge) acting as a faithful connection (see FIG. 12 below).
  • thermoelectric device manufactured according to each substrate was measured using a 4 probe facility, and the device resistivity ( ⁇ ) was measured. Table 2 shows each.
  • Example 1 1st Cu dendrite 2.00 2.03 2.02 2.02
  • Example 2 1.98 1.98 1.99 1.98
  • Example 3 1.93 1.94 1.95 1.94
  • Example 4 1.84 1.85 1.86 1.85
  • Example 5 1.82 1.81 1.82 1.81
  • Example 6 1.88 1.87 1.88 1.88
  • Example 7 2.01 2.00 2.02 2.01
  • Example 8 2.12 2.10 2.08 2.10
  • Example 9 Ag coated Cu dendrite 1.88 1.87 1.86 1.87
  • Example 10 1.83 1.83 1.83
  • Example 11 1.80 1.80 1.80 1.80
  • Example 12 2nd Cu dendrite 2.13 2.14 2.15 2.14
  • Example 13 2.19 2.20 2.20 2.20
  • the resistance value decreased when 10 to 20 ⁇ m class copper dendrite was added, compared to Comparative Example 1, and 10% silver (Ag) coated copper dendrite
  • the effect of reducing the resistance value was large.
  • Comparative Example 2 using a spherical Cu powder the effect of reducing the resistance value of the device was more excellent when 10 to 20 ⁇ m class copper dendrites were added. It is believed that the surface contact of copper dendrites has a larger contact area than the point contact of copper spherical powder, thereby improving conductivity.
  • the addition amount of Cu dendrite is suitable within the range of 1 to 40 wt%, especially when 5 to 30 wt% is added, the effect of reducing the resistance of the thermoelectric element is large.
  • the effect of reducing the resistance was not relatively large when the length of 20 ⁇ 30 ⁇ m Cu dendrite was added, which shows that the melting effect of Sn-based solder is hindered and the effect of reducing resistance is lower than that of 10 ⁇ 20 ⁇ m Cu dendrite. there was.
  • thermoelectric element size: 40 ⁇ 40 ⁇ 3t
  • Comparative Examples 1 to 2 the output change result according to repetition was measured using an output evaluation facility, and the results are shown in the following table. It is shown in 3.
  • thermoelectric output data [Pmax(W)] of the device was obtained.
  • Example 1 Metal dendrites One 2 3 Average Example 1 1st Cu dendrite 9.71 9.78 9.82 9.77 Example 2 9.98 10.02 9.90 9.97 Example 3 10.21 10.11 10.10 10.14 Example 4 10.75 10.72 10.70 10.72 Example 5 11.06 11.11 11.03 11.07 Example 6 10.52 10.56 10.45 10.51 Example 7 9.77 9.81 9.76 9.78 Example 8 9.37 9.45 9.47 9.43 Example 9 Ag coated Cu dendrite 10.60 10.59 10.63 10.61 Example 10 10.90 10.85 10.79 10.85 Example 11 11.02 11.12 11.10 11.08 Example 12 2nd Cu dendrite 9.42 9.36 9.38 9.39 Example 13 9.19 9.15 9.10 9.15 Example 14 9.04 9.09 9.11 9.08 Comparative Example 1 - 9.57 9.64 9.55 9.59 Comparative Example 2 Cu spherical 10.04 10.02 9.97 10.01
  • the output value increased when 10 ⁇ 20 ⁇ m class Cu dendrite was added as compared to Comparative Example 1, and in the case of 10% Ag coated Cu dendrite, the output value increased compared to the effect of reducing the resistance value. Insufficient.
  • the output value of the device increased when 10 to 20 ⁇ m-class copper dendrites were added.
  • the output value of the device did not improve when a Cu dendrite with a length of 20 to 30 ⁇ m was added (see Table 3 above).
  • the output evaluation was mounted on an output evaluation facility using each manufactured thermoelectric element, and a load of about 60 kgf was applied. After that, the temperature of the high-temperature portion was maintained at 300 degrees, and the temperature of the low-temperature cooling portion was maintained at 30 degrees, and then maintained for 100 hours to obtain data.

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Abstract

La présente invention concerne un élément thermoélectrique et une pâte à braser comprise dans cet élément thermoélectrique. L'invention concerne plus particulièrement un élément thermoélectrique ayant un rendement amélioré et une fiabilité à haute température améliorée en fonction d'une modification apportée à un matériau liant.
PCT/KR2019/011071 2018-12-17 2019-08-29 Élément thermoélectrique et pâte à braser comprise dans celui-ci WO2020130282A1 (fr)

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KR1020190034437A KR102149098B1 (ko) 2018-12-17 2019-03-26 열전 소자 및 이에 포함되는 솔더 페이스트
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CN113369623A (zh) * 2021-06-30 2021-09-10 哈尔滨工业大学（深圳） 一种高服役温度的半赫斯勒热电材料的钎焊连接方法

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JP2002314241A (ja) * 2001-04-18 2002-10-25 Hitachi Ltd 電子機器
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KR20130073995A (ko) * 2006-03-09 2013-07-03 신닛테츠스미킹 마테리알즈 가부시키가이샤 무연 솔더 합금, 솔더 볼 및 전자 부재와, 자동차 탑재 전자 부재용 무연 솔더 합금, 솔더 볼 및 전자 부재
WO2014084363A1 (fr) * 2012-11-29 2014-06-05 京セラ株式会社 Module thermoélectrique
KR20170071354A (ko) * 2015-12-15 2017-06-23 주식회사 엘지화학 금속 페이스트 및 열전 모듈

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JP2002314241A (ja) * 2001-04-18 2002-10-25 Hitachi Ltd 電子機器
KR20130073995A (ko) * 2006-03-09 2013-07-03 신닛테츠스미킹 마테리알즈 가부시키가이샤 무연 솔더 합금, 솔더 볼 및 전자 부재와, 자동차 탑재 전자 부재용 무연 솔더 합금, 솔더 볼 및 전자 부재
KR20130009592A (ko) * 2011-07-13 2013-01-23 미쓰이 긴조꾸 고교 가부시키가이샤 덴드라이트상 구리분
WO2014084363A1 (fr) * 2012-11-29 2014-06-05 京セラ株式会社 Module thermoélectrique
KR20170071354A (ko) * 2015-12-15 2017-06-23 주식회사 엘지화학 금속 페이스트 및 열전 모듈

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113369623A (zh) * 2021-06-30 2021-09-10 哈尔滨工业大学（深圳） 一种高服役温度的半赫斯勒热电材料的钎焊连接方法
CN113369623B (zh) * 2021-06-30 2022-06-03 哈尔滨工业大学（深圳） 一种高服役温度的半赫斯勒热电材料的钎焊连接方法

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